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WO2009066115A1 - Sondes colorimétriques pour la détection de l'anion fluorure dans une solution et un gel - Google Patents

Sondes colorimétriques pour la détection de l'anion fluorure dans une solution et un gel Download PDF

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Publication number
WO2009066115A1
WO2009066115A1 PCT/HR2008/000016 HR2008000016W WO2009066115A1 WO 2009066115 A1 WO2009066115 A1 WO 2009066115A1 HR 2008000016 W HR2008000016 W HR 2008000016W WO 2009066115 A1 WO2009066115 A1 WO 2009066115A1
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WO
WIPO (PCT)
Prior art keywords
oxalamide
solution
gel
amino acid
general formula
Prior art date
Application number
PCT/HR2008/000016
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English (en)
Inventor
Zoran Dzolic
Mladen Zinic
Massimo Cametti
Antonella Dalla Cort
Luigi Mandolini
Original Assignee
Ruder Boskovic Institute
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Filing date
Publication date
Application filed by Ruder Boskovic Institute filed Critical Ruder Boskovic Institute
Publication of WO2009066115A1 publication Critical patent/WO2009066115A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/56—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having carbon atoms of carboxamide groups bound to carbon atoms of carboxyl groups, e.g. oxamides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators

Definitions

  • This invention relates to oxalamide derivatives of anthraquinone, their preparation procedure, use of compounds described herein in detection of fluoride anion in suspension and gel.
  • the invention furthermore relates to intermediates in preparation procedures of oxalamide derivatives of anthraquinone.
  • fluoride anion is extremely important for the preservation of bone stability and firmness of teeth enamel. Excessive dose of fluoride anion may, especially in children, cause damage and change in colour of teeth enamel, loss of hair and skin inflammation.
  • C. B. Black, B. Andrioletti A. C. Try, C. Ruiperez and J. L. Sessler, J. Am. Chem. Soc, 1999, 121, 10438-10439.
  • Sensors are mostly compounds containing amide, urea or thiourea groups, which act as a multiple hydrogen bond donors thus enabling target anion binding.
  • Certain organic molecules of low molecular mass can thermoreversibly gelate water and numerous organic solvents. Gels are created by dissolving small amounts of gelator molecules in hot solvent and then cooling down below the gelation temperature. This causes an immobilisation of total solvent volume and loss of fluidity. Interest for preparation of these compounds has increased due to their microscopic and macroscopic properties and great application possibilities in various areas: biomedicine, different technologies and environment protection.
  • Oxalamide moiety is incorporated in known chiral amino acid and amino alcohol organo- and hydrogelators.
  • Z. Dzolic, K. Wolsperger and M. Zinic New J. Chem., 2006, 30, 141 1-1419; S. Miljanic, L. Frkanec, T. Biljan, Z. Meic and M. Zinic, Langmuir, 2006, 22, 9079-9081; S. Miljanic, L. Frkanec, Z. Meic and M. Zinic, Eur. J. Org. Chem., 2006, 1323-1334; S. Miljanic, L.
  • Subject of the present invention relates to new oxalamide derivatives of anthraquinone, their preparation procedure and their usage in recognition and detection of fluoride anion in solvent and gel.
  • the subject of this invention furthermore relates to the intermediates in preparation of oxalamide derivatives of anthraquinone: oxamate amino acid derivatives and oxalamide amino acid derivatives and their preparation procedures.
  • Ri is a branched or straightchained Ci -6 alkyl group, phenyl, benzyl or ⁇ -hydroxybenzyl
  • R 2 is a hydrogen, branched or straightchained C) -6 alkyl group, benzyl or M +
  • n represents an integer from 1 to 9 and their optical isomers and mixtures.
  • the subject of the invention also relates to the preparation procedure of the oxalamide derivatives of anthraquinone, shown in the reaction scheme (scheme 1), which includes reaction of amino acid and ethyl oxalyl chloride, reaction of oxamate amino acid derivative with N-benzyl dialkylamine, hydrogenation of oxalamide amino acid derivative, condensation of amine of oxalamide amino acid derivative with ethyl-N-1-anthraquinone oxamate and isolation of oxalamide derivative of anthraquinone from reaction mixture through precrystallization, which is defined by the below mentioned general preparation procedure:
  • Ri is a branched or straightchained Ci -6 alkyl group, phenyl, benzyl or/7-hydroxybenzyl
  • R 2 is a hydrogen, branched or straightchained Ci -6 alkyl group, benzyl or M +
  • n represents an integer from 1 to 9 and their optical isomers and their mixtures include the following steps: Step a) preparation of oxamate amino acid derivatives with general formula II
  • oxalamide amino acid derivative III In a reaction flask 1 equivalent of oxalamide amino acid derivative III is dissolved in a suitable organic solvent. Catalyst is added to this solution and reaction mixture is hydrogenated under hydrogen stream at room temperature for at least one hour. The reaction progress is monitored by thin layer chromatography on silica gel. After filtration through Celite, organic solvent is evaporated by distillation under reduced pressure. Isolated amine of oxalamide amino acid derivative is used without further purification.
  • a suitable organic solvent 1 equivalent of ethyl- N-I -anthraquinone oxamate is dissolved. To this solution, the solution of obtained amine of oxalamide amino acid derivative is added at room temperature under nitrogen. Reaction mixture is stirred at least for 48 hours at room temperature. Precipitated product is filtered off and purified by precrystallisation from organic solvent.
  • the subject of this invention is also the use of compounds with general formula I for fluoride anion detection.
  • Oxalamide derivatives of anthraquinone shown herein are binding fluoride anion in solution and gel.
  • the binding of fluoride anion in solution is demonstrated by UV-Vis titration and shown in test of anion binding in solution. This phenomenon is accompanied by visible colour change from yellow into red ( Figure 1).
  • the binding of fluoride anion in gel is shown in test of fluoride anion binding and the diffusion of Bu 4 NF solution through gel prepared from oxalamide derivative of anthraquinone I.
  • the presence of fluoride anion results in changes in gel colour and morphology (phase change from gel to liquid) caused by specific recognition of fluoride anion.
  • Compounds with general formula I and mixtures containing at least one of the mentioned compounds are also used for extraction of anions.
  • Fluoride anion binding is characterised by appearance of a new band at
  • Ethyl 7V-(L-Leucine methyl ester)oxamate (1) Ethyl 7V-(L-Leucine methyl ester)oxamate (1).
  • Ethyl oxalyl chloride (3.35 cm 3 , 30 mmol) in anhydrous dichloromethane (20 cm 3 ) is added dropwise to the mixture of L-leucine methyl ester hydrochloride (5 g, 27.5 mmol) and triethylamine (8.1 cm 3 , 58 mmol) in anhydrous dichloromethane (100 cm 3 ) over 1 hour at 0 0 C.
  • EXAMPLE 2 iV-(L-Leucine methyl ester)-iV'-(7V-benzylethylenediamine)oxalamide (2).
  • Mixture of ethyl N- (L-Leucine methyl ester)oxamate 1 (2 g, 8.2 mmol) and N-benzylethylendiamine (1.37 g, 9.1 mmol) is stirred in anhydrous dichloromethane (50 cm 3 ) overnight at room temperature under nitrogen atmosphere.
  • the reaction mixture is successively washed with water (2 x 20 cm 3 ), saturated aqueous solution of ammonium chloride (2 x 20 cm 3 ) and water (3 x 20 cm 3 ).
  • Organic layer is dried over anhydrous natrium sulphate and solvent is evaporated.
  • Crude product is purified by column chromatography on silica gel (CH 2 Cl 2 ZCH 3 OH 3:1) to obtain compound 2 (2.5 g, 87%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

L'invention concerne des dérivés oxalamide d'anthraquinone de la formule générale (I), leur procédure de préparation et leur utilisation pour lier des anions fluorures dans une solution et un gel. Les anions entraînent un changement de la couleur de la solution et un changement de la couleur et de la morphologie du gel (changement de phase du gel au liquide).
PCT/HR2008/000016 2007-05-15 2008-05-15 Sondes colorimétriques pour la détection de l'anion fluorure dans une solution et un gel WO2009066115A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HR20070225A HRP20070225A2 (en) 2007-05-15 2007-05-15 Colorimetric sensors for detection of fluoride anion in solution and gel
HRP20070225A 2007-05-15

Publications (1)

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WO2009066115A1 true WO2009066115A1 (fr) 2009-05-28

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HR (1) HRP20070225A2 (fr)
WO (1) WO2009066115A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102466635A (zh) * 2010-11-17 2012-05-23 中国科学院化学研究所 异噁唑类化合物在氟离子检测中的用途
US8541240B2 (en) 2010-05-28 2013-09-24 Florida State University Research Foundation, Inc. Colorimetric and fluorimetric fluoride sensing
CN113138189A (zh) * 2021-04-22 2021-07-20 中国石油大学(华东) 一种AgPt-Fe3O4@SiO2纳米粒子探针用于比色检测氟离子的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087640A1 (fr) * 2003-04-04 2004-10-14 Dsm Ip Assets B.V. Procede de fabrication de n-alkoxalyl-alaninates

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087640A1 (fr) * 2003-04-04 2004-10-14 Dsm Ip Assets B.V. Procede de fabrication de n-alkoxalyl-alaninates

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DZOLIC, CAMETTI, DALLA CORT, MANDOLINI, ZINIC: "Fluoride-responsive organogelator based on oxalamide-derives anthraquinone", CHEMICAL COMMUNICATIONS, 6 August 2007 (2007-08-06), pages 3535 - 3537, XP009106118 *
DZOLIC, WOLSPERGER, ZINIC: "Synergic effect in gelation by two-component mixture of chiral gelators", NEW JOURNAL OF ORGANIC CHEMISTRY, vol. 30, 2006, pages 1411 - 1419, XP002497065 *
JOSE, KUMAR, GANGULY, DAS: "Efficient and simple colorimetric fluoride ion sensor based on receptors having urea and thiourea binding sites.", ORGANIC LETTERS, vol. 6, no. 20, 2004, pages 3445 - 3448, XP002497064 *
MAEDA I ET AL: "THE SYNTHETIC INTERMEDIATE OF PYRIDOXINE. III. THE SIMPLE SYNTHESIS OF ETHYL N-ETHOXYALYLALANINATE AND ETHYL N-FORMYLALANINATE", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, CHEMICAL SOCIETY OF JAPAN, TOKYO, JP, vol. 45, 1 June 1972 (1972-06-01), pages 1917/1918, XP009033337, ISSN: 0009-2673 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541240B2 (en) 2010-05-28 2013-09-24 Florida State University Research Foundation, Inc. Colorimetric and fluorimetric fluoride sensing
CN102466635A (zh) * 2010-11-17 2012-05-23 中国科学院化学研究所 异噁唑类化合物在氟离子检测中的用途
CN102466635B (zh) * 2010-11-17 2013-08-21 中国科学院化学研究所 异噁唑类化合物在氟离子检测中的用途
CN113138189A (zh) * 2021-04-22 2021-07-20 中国石油大学(华东) 一种AgPt-Fe3O4@SiO2纳米粒子探针用于比色检测氟离子的方法
CN113138189B (zh) * 2021-04-22 2022-08-19 中国石油大学(华东) 一种AgPt-Fe3O4@SiO2纳米粒子探针用于比色检测氟离子的方法

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